Three coordinate aluminum catalyst activator composition

ABSTRACT

Catalyst compositions useful for olefin polymerizations comprising a Group 3-10 metal complex and a compound corresponding to the formula: AlAr f Q 1 Q 2 , or a dimer, adduct, or mixture thereof and further mixtures with aluminum compounds of the formula AlAr f   3 , where: 
     Ar f  is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms; 
     Q 1  is Ar f  or a C 1-20  hydrocarbyl group, optionally substituted with one or more cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, further optionally, such substituents may be covalently linked with each other to form one or more fused rings or ring systems; and 
     Q 2  is an aryloxy, arylsulfide or di(hydrocarbyl)amido group, optionally substituted with one or more hydrocarbyl, cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, further optionally such substituents may be covalently linked with each other to form one or more fused rings or ring systems, said Q 2  having from 3 to 20 atoms other than hydrogen are useful as activators for olefin polymerizations.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional from U.S. application Ser. No.09/330,671, filed Jun. 11, 1999, now U.S. Pat. No. 6,187,940 whichclaims benefit from provisional applications No. 60/096,801, filed Aug.17,1998, and No. 60/100,487, filed Sept. 16, 1998.

BACKGROUND OF THE INVENTION

The present invention relates to compositions that are useful ascatalyst activators for olefin polymerizations. More particularly thepresent invention relates to such compositions that are particularlyadapted for use in the coordination polymerization of unsaturatedcompounds having improved activation efficiency and performance. Suchcompositions are particularly advantageous for use in a polymerizationprocess wherein catalyst, catalyst activator, and at least onepolymerizable monomer are combined under polymerization conditions toform a polymeric product.

It is previously known in the art to activate Ziegler-Nattapolymerization catalysts, particularly such catalysts comprising Group3-10 metal complexes containing delocalized π-bonded ligand groups, bythe use of an activator. Generally in the absence of such an activatorcompound, also referred to as a cocatalyst, little or no polymerizationactivity is observed.

A class of suitable activators are Lewis acids, especially alumoxanes,which are generally believed to be oligomeric or polymericalkylaluminoxy compounds, including cyclic oligomers. Examples ofalumoxanes (also known as aluminoxanes) include methylalumoxane (MAO)made by hydrolysis of trimethylaluminum as well as modifiedmethylalumoxane (MMAO), wherein a portion of the trimethylaluminum inthe foregoing hydrolysis is replaced by a higher trialkylaluminumcompound such as triisobutylaluminum. MMAO advantageously is moresoluble in aliphatic solvents than is MAO.

Generally alumoxanes contain on average about 1.5 alkyl groups peraluminum atom, and are prepared by reaction of trialkylaluminumcompounds or mixtures of compounds with water (Reddy et al, Prog. Poly.Sci., 1995, 20, 309-367). The resulting product is in fact a mixture ofvarious substituted aluminum compounds including especially,trialkylaluminum compounds (resulting from incomplete reaction of thetrialkylaluminum starting reagent or decomposition of the alumoxane).The amount of such free trialkylaluminum compound in the mixturegenerally varies from 1 to 50 percent by weight of the total product.

Although effective in forming an active olefin polymerization catalystwhen combined with a variety of Group 3-10 metal complexes, especiallyGroup 4 metal complexes, generally a large excess of alumoxane comparedto metal complex, such as, molar ratios from 100:1 to 10,000:1, isrequired in order to produce adequate rates of polymerization.Unfortunately, the use of such large excesses of cocatalyst is expensiveand also results in polymer having an elevated residual aluminum contentas well as lower molecular weight. This former factor may adverselyaffect polymer properties, especially clarity and dielectric constant,whereas the latter issue relates to poor polymer performance.

Other types of monomeric aryloxyaluminum and arylamidoaluminum complexeshave been found to be useful in metallocene catalyst activator packages,particularly as water and oxygenate scavengers. Examples includediisobutyl-2,6-di-t-butyl-4-methylphenoxyaluminum (DIBAL-BOT) asdescribed in WO 97/27228 and Japanese kokai, 09-17629, ordiisobutylhexamethyldisilylazayl aluminum (DIBAL-NS) as described byRosen et al in WO 98/03558. Typically in such formulations, the Lewisacid, especially tris(pentafluorophanyl)borane, is first contacted witha metal complex to prepare the catalytically activated derivative.Thereafter, this derivative is generally not subject to ligand transferwith the aluminum compound.

A different type of activator compound is a Bronsted acid salt capableof transferring a proton to form a cationic derivative or othercatalytically active derivative of such Group 3-10 metal complex,cationic charge transferring compounds, or cationic oxidizingactivators, referred to collectively hereinafter as cationic activators.Preferred cationic activators are ammonium, sulfonium, phosphonium,oxonium, ferrocenium, silver, lead, carbonium or silylium compoundscontaining a cation/anion pair that is capable of rendering the Group3-10 metal complex catalytically active. Preferred anions associatedwith this cation comprise fluorinated arylborate anions, morepreferably, the tetrakis(pentafluorophenyl)borate anion. Additionalsuitable anions include sterically shielded, bridged diboron anions.Examples of such cationic activators are disclosed in U.S. Pat. Nos.5,198,401, 5,132,380, 5,470,927, 5,153,157, 5,350,723, 5,189,192,5,626,087 and in 5,447,895.

Further suitable activators for activating metal complexes for olefinpolymerization include neutral Lewis acids such astris(perfluorophenyl)borane and tris-(perfluorobiphenyl)borane. Theformer composition has been previously disclosed for the above statedend use in U.S. Pat. No. 5,721,185, and elsewhere, whereas the lattercomposition is disclosed in Marks, et al, J. Am. Chem. Soc. 1996, 118,12451-12452. Additional teachings of the foregoing activators may befound in Chen, et al, J. Am. Chem. Soc. 1997, 119, 2582-2583, Jia et al,Organometallics, 1997, 16, 842-857, and Coles et al, J. Am. Chem. Soc.1997, 119, 8126-8126.

Tris(perfluorophenyl)aluminum is a strong Lewis acid as well. It hasrecently been prepared from the exchange of tris(perfluorophenyl)boranewith trialkylaluminum, which gives a trialkylborane andtris-perfluorophenylaluminum, as described by Biagini et al U.S. Pat.No. 5,602,269. However, it generally performs poorly by itself as acatalyst activator compared with tris(perfluorophenyl)borane when usedin an equimolar ratio with a metal complex. Similarly, It has furtherbeen demonstrated that active catalysts resulting from the use of analuminate anion based upon tris-(perfluorophenyl)aluminum for theactivation of ansa-metallocenes and biscyclopentadienyl derivatives ofzirconium(IV) are generally of lower activity than those formed by thecorresponding borane (Ewen, Stud. in Surf. Sci. Catal. 1994, 89,405-410). A possible explanation for the poor performance oftris(perfluorophenyl)aluminum as an activator for metallocenes involvinga back exchange reaction of a perfluorophenyl group has been proposed byBochmann et al (ACS Dallas Meeting, March 1998, Abs. number INOR 264,subsequently published, Organometallics, 1998, 17, 5908-5912).

In light of these apparent deficiencies, it would be desirable toprovide novel compounds having improved efficiency and operability asactivators of metal complexes for olefin polymerizations.

SUMMARY OF THE INVENTION

According to the present invention there is now provided a compoundcorresponding to the formula: AlAr^(f)Q¹Q², or a dimer, adduct, ormixture thereof; where:

Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30carbon atoms;

Q¹ is Ar^(f) or a C₁₋₂₀ hydrocarbyl group, optionally substituted withone or more cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl,di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino,di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to20 atoms other than hydrogen, or, further optionally, such substituentsmay be covalently linked with each other to form one or more fused ringsor ring systems; and

Q² is an aryloxy, arylsulfide or di(hydrocarbyl)amido group, optionallysubstituted with one or more hydrocarbyl, cyclohydrocarbyl,hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,hydrocarbylsilyl, silylhydrocarbyl, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, further optionally such substituents may be covalently linked witheach other to form one or more fused rings or ring systems, said Q²having from 3 to 20 atoms other than hydrogen.

The subject invention further provides a method for preparing theforegoing compound comprising contacting under ligand exchange reactionconditions a trifluoroarylaluminum or trifluoroarylboron compound of theformula Ar^(f) ₃Me¹,

wherein Ar^(f) is as previously defined, and

Me¹ is aluminum or boron,

with a Group 13 organometallic compound of the formula: Q³ ₂Me²Q²,wherein

Q² is as previously defined;

Q³ is independently each occurrence C₁₋₄ alkyl; and

Me² is a Group 13 metal, with the proviso that if Me¹ is boron, then Me²is aluminum.

In a particular embodiment of the foregoing method for preparing thecompounds, a stoichiometric excess of the Group 13 organometalliccompound of the formula: Q³ ₂Me²Q² is employed in the ligand exchangereaction. The resulting reaction mixture accordingly does not includesignificant quantities of residual trifluoroarylaluminum ortrifluoroarylboron compound.

The subject invention further provides a catalyst composition forpolymerization of olefins comprising a Group 3-10 metal complex and anactivator comprising the above described compound or composition, themolar ratio of metal complex to activator in the catalyst compositionbeing from 0.1:1 to 3:1.

The subject invention further provides a process for the polymerizationof one or more addition polymerizable monomers comprising contacting oneor more addition polymerizable monomers under addition polymerizationconditions with the catalyst composition as described above.

These and other embodiments are more fully described in the followingdetailed description.

DETAILED DESCRIPTION

All references herein to elements belonging to a certain Group refer tothe Periodic Table of the Elements published and copyrighted by CRCPress, Inc., 1995. Also any reference to the Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. The full teachings of anypatent, patent application, provisional application, or publicationreferred to herein are hereby incorporated by reference.

Preferred compositions according to the present invention are thosewherein Ar is a perfluoroaryl group, more preferably a perfluorophenylgroup, Q¹ is C₃₋₆ alkyl containing at least one secondary or tertiarycarbon center, more preferably isopropyl or isobutyl, and Q² is aryloxyor dialkylamido of up to 10 carbons, more preferably2,6-di-(t-butyl)phenoxy, 2,6-di-(t-butyl)-4-methylphenoxy,N,N-bis(trimethylsilyl)amido, or N,N-dimethylamido. Most preferredcompounds are monomers, rather than dimers or adducts.

In another preferred embodiment, the foregoing compounds are prochiraland optically inactive, however four coordinate derivatives thereof arechiral.

A most preferred aluminum compound formed according to the invention isisobutyl(perfluorophenyl)-2-methyl-4,6-di-(t-butyl)phenoxyaluminum orisobutyl(perfluorophenyl)-4,6-di-(t-butyl)phenoxyaluminum.

In a preferred process for making the compounds of the invention theexchange reaction is conducted in an aliphatic, cycloaliphatic oraromatic hydrocarbon liquid or mixture thereof under anhydrousconditions. Preferably, the Group 13 organometallic compound is analuminum compound and is provided in a stoichiometric excess withrespect to the trifluoroaryl aluminum or trifluoroaryl boron compound,more preferably at a molar ratio from 1:1 to 20:1, most preferably from1:1 to 10:1. Preferred are the use of solutions of the foregoingreactants in concentrations of fluoroaryl compound and Group 13 compoundfrom 0.005 to 2M, preferably from 0.02 to 1.5 M, and most preferablyfrom 0.05 to 1.2 M. Generally, the Group 13 organometallic compoundreadily transfers one Q³ group. However, the rate of transfer of asecond Q³ group is kinetically disfavored, thereby allowing for therecovery of the desired product in high yield and efficiency.

The rate of ligand exchange can be enhanced by heating the reactionmixture or by removing any alkyl exchange byproducts in the reactionmixture, especially any trialkylborane byproducts. A preferredtemperature range for the exchange reaction is from 0 to 50° C., morepreferably from 15 to 35° C. Suitable techniques for removing alkylexchange byproducts from the reaction mixture include degassingoptionally at reduced pressures, distillation, solvent exchange, solventextraction, extraction with a volatile agent, contacting with a zeoliteor molecular sieve, and combinations of the foregoing techniques, all ofwhich are conducted according to conventional procedures. Purity of theresulting product may be determined by analysis of the reaction mixture.Desirably the content of trialkylboron compound in the compounds of theinvention is less than 1 percent by weight, preferably less than 0.1percent by weight. Removal of volatile by-products will assist inshifting the equilibrium concentration of desired end products.Generally, reaction times from 10 minutes to 6 hours, preferably 15minutes to 1 hour are used to ensure formation of the desired ligandexchange products.

In as much as the present compounds are desirably prepared by anexchange reaction as previously described, it is to be understood thatthe resulting product mixture may include species in addition to thoseof the formula, AlAr^(f)Q¹Q². Additional components may include startingreactants as well as alternative exchange products. It is to beunderstood that the compounds of the invention may be prepared and usedin the form of such a mixture of compounds. More particularly,alternative exchange products and starting reactants that may be foundin such a mixture include compounds corresponding to the formula: [Me¹Q¹₃] where:

Q¹ is Ar^(f) or a C₁₋₂₀ hydrocarbyl group, optionally substituted withone or more cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl,di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino,di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to20 atoms other than hydrogen, or, further optionally, such substituentsmay be covalently linked with each other to form one or more fused ringsor ring systems;

Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30carbon atoms; and

Me¹ is boron or aluminum, especially aluminum.

The exchange process is more particularly illustrated by reference tothe following particular embodiment.(Isobutyl)(perfluorophenyl)(2-methyl-4,6-di-t-butylphenoxy)aluminum,which has been found to be an effective and useful cocatalyst for use inolefin polymerizations in combination with a group 4 metal complex, maybe prepared by reacting tris(perfluorophenyl)borane (FAB) withdiisobutyl-2,6-di-t-butyl-4-methylphenoxyaluminum (DIBAL-BOT) in asuitable diluent, preferably a hydrocarbon liquid. Preferably, theDIBAL-BOT is provided in stoichiometric excess with respect to the FAB.Further preferably, the two reagents are combined in solutions havingconcentrations of at least 0.005 M, preferably at least 0.05 M, morepreferably at least 0.02 M; and, for reasons of solubility, typically nomore than 2 M, preferably, no more than 1.5 M, and most preferably nomore than 1.2 M. The use of excess Di-BAL-BOT insures the production oftri-coordinate aluminum species and likewise efficiently distributes allof the costly perfluoroaryl groups to aluminum, the co-product beingmainly triisobutylboron, as illustrated in the following reactionscheme:

The rate of exchange reaction can be conveniently monitored by ¹⁹F and¹H NMR spectroscopy to ensure complete reaction.

In an alternate preferred embodiment of the invention, the activatorisobutylperfluorophenyl-2-methyl-4,6-di-t-butylphenoxyaluminum, isprepared by reacting tris-(perfluorophenyl)aluminum (FAAL, whichtypically exists as a stoichiometric toluene solvate) with DiBAL-BOT ina hydrocarbon or aromatic solvent to produce theisobutylperfluorophenyl-2-methyl-4,6-di-t-butylphenoxyaluminum via anintermediate species, bis-perfluorophenylisobutylaluminum. Thisalternate embodiment of the invention is illustrated by the followingreaction scheme:

In this process, lower ratios of FAAL:DIBALBOT (1:1-1:2) form a highlyactive formulation, consisting of essentially two active aluminumcomponents, bis-perfluorophenylisobutyl-aluminum and(perfluorophenyl)(isobutyl)(2-methyl-4,6-di-t-butylphenoxy)aluminum. Ithas now been determined that the partial exchange product,bis-perfluorophenylisobutylaluminum, is a highly active cocatalyst foruse with group 4 metal complexes in an olefin polymerization. The use ofhigher ratios of DIBAL-BOT to FAAL (5-10:1) favors extinction ofbisperfluorophenylisobutylaluminum and increases the amount ofisobutylperfluorophenyl-2-methyl-4,6-di-t-butylphenoxyaluminum in themixture. These ratios are not intended to limit the nature of theinvention and may provide a suitable means for tailoring the efficiencyof broad classes of metal complexes which may require a combination ofthese activators.

The present composition provides a highly active co-catalyst for use inactivation of metal complexes, especially Group 4 metallocenes for thepolymerization of olefins. In such use it is desirably employed as adilute concentration in a hydrocarbon liquid, especially an aliphatichydrocarbon liquid for use as a homogeneous catalyst, especially forsolution polymerizations. Additionally, the composition may be depositedon an inert support, especially a particulated metal oxide or polymer,in combination with the metal complex to be activated according to knowntechniques for producing supported olefin polymerization catalysts, andthereafter used for gas phase or slurry polymerizations.

The present compounds and compositions provide highly activeco-catalysts for use in activation of metal complexes, especially Group4 metallocenes for the polymerization of olefins. In such use they aredesirably employed as a dilute solution in a hydrocarbon liquid,especially an aliphatic hydrocarbon liquid for use as a homogeneouscatalyst, especially for solution polymerizations. Additionally, thecompound, or composition may be deposited on an inert support,especially a particulated metal oxide or polymer, in combination withthe metal complex to be activated according to known techniques forproducing supported olefin polymerization catalysts, and thereafter usedfor gas phase or slurry polymerizations.

When in use as a catalyst activator, the molar ratio of metal complex toactivator composition is preferably from 0.1:1 to 3:1, more preferablyfrom 0.2:1 to 2:1, most preferably from 0.25:1 to 1:1, based on themetal contents of each component. In most polymerization reactions themolar ratio of metal complex: polymerizable compound employed is from10⁻¹²:1 to 10⁻¹:1, more preferably from 10⁻¹²:1 to 10⁻⁵:1.

The support for the activator component may be any inert, particulatematerial, but most suitably is a metal oxide or mixture of metal oxides,preferably alumina, silica, an aluminosilicate or clay material.Suitable volume average particle sizes of the support are from 1 to 1000μM, preferably from 10 to 100 μM. Most desired supports are calcinedsilica, which may be treated prior to use to reduce surface hydroxylgroups thereon, by reaction with a silane, a trialkylaluminum, orsimilar reactive compound. Any suitable means for incorporating theperfluoroaryl)aluminum co-catalyst mixture onto the surface of a supportmay be used, including dispersing the co-catalyst in a liquid andcontacting the same with the support by slurrying, impregnation,spraying, or coating and thereafter removing the liquid, or by combiningthe cocatalyst and a support material in dry or paste form andintimately contacting the mixture, thereafter forming a dried,particulated product.

Suitable metal complexes for use in combination with the foregoingcocatalysts include any complex of a metal of Groups 3-10 of thePeriodic table of the Elements capable of being activated to polymerizeaddition polymerizable compounds, especially olefins by the presentactivators. Examples include Group 10 diimine derivatives correspondingto the formula:

wherein

M* is Ni(II) or Pd(II);

X′ is halo, hydrocarbyl, or hydrocarbyloxy;

Ar* is an aryl group, especially 2,6-diisopropylphenyl or aniline group;and

CT—CT is 1,2-ethanediyl, 2,3-butanediyl, or form a fused ring systemwherein the two T groups together are a 1,8-naphthanediyl group.

Similar complexes to the foregoing are disclosed by M. Brookhart, etal., in J. Am. Chem. Soc., 118, 267-268 (1996) and J. Am. Chem. Soc.,117, 6414-6415 (1995), as being suitable for forming activepolymerization catalysts especially for polymerization of α-olefins,either alone or in combination with polar comonomers such as vinylchloride, alkyl acrylates and alkyl methacrylates.

Additional complexes include derivatives of Group 3, 4, or Lanthanidemetals containing from 1 to 3 π-bonded anionic or neutral ligand groups,which may be cyclic or non-cyclic delocalized π-bonded anionic ligandgroups. Exemplary of such π-bonded anionic ligand groups are conjugatedor nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups,boratabenzene groups, phosphoyl groups and arene groups. By the term“π-bonded” is meant that the ligand group is bonded to the transitionmetal by a sharing of electrons from a delocalized π-bond.

Each atom in the delocalized 7u-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyloxy,hydrocarbylsulfide, dihydrocarbylamino, and hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements, and such hydrocarbyl-,halohydrocarbyl-, hydrocarbyloxy-, hydrocarbylsulfide-,dihydrocarbylamino- or hydrocarbyl-substituted metalloid-radicals thatare further substituted with a Group 15 or 16 hetero atom containingmoiety. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substituted alkylradicals. In addition two or more such radicals may together form afused ring system, including partially or fully hydrogenated fused ringsystems, or they may form a metallocycle with the metal. Suitablehydrocarbyl-substituted organometalloid radicals include mono-, di- andtri-substituted organometalloid radicals of Group 14 elements whereineach of the hydrocarbyl groups contains from 1 to 20 carbon atoms.Examples of suitable hydrocarbyl-substituted organometalloid radicalsinclude trimethylsilyl, triethylsilyl, ethyidimethylsilyl,methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamine, phosphine, ether or thioether moieties or divalent derivativesthereof, for example amide, phosphide, ether or thioether groups bondedto the transition metal or Lanthanide metal, and bonded to thehydrocarbyl group or to the hydrocarbyl-substituted metalloid containinggroup.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,and boratabenzene groups, as well as C₁₋₁₀ hydrocarbyl-substituted,C₁₋₁₀ hydrocarbyloxy-substituted, di(C₁₋₁₀hydrocarbyl)amino-substituted, or tri(C₁₋₁₀hydrocarbyl)silyl-substituted derivatives thereof. Preferred anionicdelocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.

The boratabenzenes are anionic ligands which are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Herberich, et al., in Organometallics, 1995, 14, 1,471-480. Preferred boratabenzenes correspond to the formula:

wherein R″ is selected from the group consisting of hydrocarbyl, silyl,or germyl, said R″ having up to 20 non-hydrogen atoms. In complexesinvolving divalent derivatives of such delocalized π-bonded groups oneatom thereof is bonded by means of a covalent bond or a covalentlybonded divalent group to another atom of the complex thereby forming abridged system.

Suitable metal complexes for use in the catalysts of the presentinvention may be derivatives of any transition metal includingLanthanides, but preferably of Group 3, 4, or Lanthanide metals whichare in the +2, +3, or +4 formal oxidation state meeting the previouslymentioned requirements. Preferred compounds include metal complexes(metallocenes) containing from 1 to 3 π-bonded anionic ligand groups,which may be cyclic or noncyclic delocalized π-bonded anionic ligandgroups. Exemplary of such π-bonded anionic ligand groups are conjugatedor nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups, andarene groups. By the term “π-bonded” is meant that the ligand group isbonded to the transition metal by means of delocalized electrons presentin a π bond.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenylgroups, as well as C₁₋₁₀ hydrocarbyl-substituted derivatives thereof.Preferred anionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and2-methyl-4-phenylindenyl.

More preferred are metal complexes corresponding to the formula:

L_(l)MX_(m)X′_(n)X″_(p), or a dimer thereof

wherein:

L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 atoms not counting hydrogen, optionally two L groupsmay be joined together through one or more substituents thereby forminga bridged structure, and further optionally one L may be bound to Xthrough one or more substituents of L;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is an optional, divalent substituent of up to 50 non-hydrogen atomsthat together with L forms a metallocycle with M;

X′ is an optional neutral Lewis base having up to 20 non-hydrogen atoms;

X″ each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or form a neutral, conjugated or nonconjugated diene that isπ-bonded to M (whereupon M is in the +2 oxidation state), or furtheroptionally one or more X″ and one or more X′ groups may be bondedtogether thereby forming a moiety that is both covalently bound to M andcoordinated thereto by means of Lewis base functionality;

l is 1 or 2;

m is 0 or 1;

n is a number from 0 to 3;

p is an integer from 0 to 3; and

the sum, l+m+p, is equal to the formal oxidation state of M.

Such preferred complexes include those containing either one or two Lgroups. The latter complexes include those containing a bridging grouplinking the two L groups. Preferred bridging groups are thosecorresponding to the formula (ER*₂)_(x) wherein E is silicon or carbon,R* independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R*having up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, R*independently each occurrence is methyl, benzyl, tert-butyl or phenyl.

Examples of the foregoing bis(L) containing complexes are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, dihydrocarbylamino,hydrocarbyleneamino, silyl, germyl, cyano, halo and combinationsthereof, said R³ having up to 20 atoms not counting hydrogen, oradjacent R³ groups together form a divalent derivative thereby forming afused ring system, and

X″ independently each occurrence is an anionic ligand group of up to 40atoms not counting hydrogen, or two X″ groups together form a divalentanionic ligand group of up to 40 atoms not counting hydrogen or togetherare a conjugated diene having from 4 to 30 atoms not counting hydrogenforming a π-complex with M, whereupon M is in the +2 formal oxidationstate, and

R*, E and x are as previously defined.

The foregoing metal complexes are especially suited for the preparationof polymers having stereoregular molecular structure. In such capacityit is preferred that the complex possess C₂ symmetry or possess achiral, stereorigid structure. Examples of the first type are compoundspossessing different delocalized π-bonded systems, such as onecyclopentadienyl group and one fluorenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980).Examples of chiral structures include bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem, 232,233-47, (1982).

Exemplary bridged ligands containing two π-bonded groups are:(dimethylsilyl-bis-cyclopentadienyl),(dimethylsilyl-bis-methylcyclopentadienyl),(dimethylsilyl-bis-ethylcyclopentadienyl,(dimethylsilyl-bis-t-butylcyclopentadienyl),(dimethylsilyl-bis-tetramethylcyclopentadienyl),(dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl),(dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl),(dimethylsilyl-bis-2-methyl-4-phenylindenyl),(dimethylsilyl-bis-2-methylindenyl),(dimethylsilyl-cyclopentadienyl-fluorenyl),(1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl),(1,2-bis(cyclopentadienyl)ethane, and(isopropylidene-cyclopentadienyl-fluorenyl).

Preferred X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

A further class of metal complexes utilized in the present inventioncorrespond to the formula:

L_(l)MX_(m)X′_(n)X″_(p), or a dimer thereof

wherein:

L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 atoms not counting hydrogen;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is a divalent substituent of up to 50 non-hydrogen atoms that togetherwith L forms a metallocycle with M;

X′ is an optional neutral Lewis base ligand having up to 20 non-hydrogenatoms;

X″ each occurrence is a monovalent, anionic moiety having up to 20non-hydrogen atoms, optionally two X″ groups together may form adivalent anionic moiety having both valences bound to M or a neutralC₅₋₃₀ conjugated diene, and further optionally X′ and X″ may be bondedtogether thereby forming a moiety that is both covalently bound to M andcoordinated thereto by means of Lewis base functionality;

l is 1 or 2;

m is 1;

n is a number from 0 to 3;

p is an integer from 1 to 2; and

the sum, l+m+p, is equal to the formal oxidation state of M.

Preferred divalent X substituents preferably include groups containingup to 30 atoms not counting hydrogen and comprising at least one atomthat is oxygen, sulfur, boron or a member of Group 14 of the PeriodicTable of the Elements directly attached to the delocalized π-bondedgroup, and a different atom, selected from the group consisting ofnitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M.

A preferred class of such Group 4 metal coordination complexes usedaccording to the present invention correspond to the formula:

wherein:

M is titanium or zirconium in the +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X″ is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, saidgroup having up to 20 atoms not counting hydrogen, or two X″ groupstogether form a C₅₋₃₀ conjugated diene;

Y is —O—, —S—, —NR*—, —PR*—; and

Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, or GeR*₂,wherein: R* is as previously defined.

Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention include:

cyclopentadienyltitaniumtrimethyl,

cyclopentadienyltitaniumtriethyl,

cyclopentadienyltitaniumtriisopropyl,

cyclopentadienyltitaniumtriphenyl,

cyclopentadienyltitaniumtribenzyl,

cyclopentadienyltitanium-2,4-pentadienyl,cyclopentadienyltitaniumdimethylmethoxide,

cyclopentadienyltitaniumdimethylchloride,pentamethylcyclopentadienyltitaniumtrimethyl,

indenyltitaniumtrimethyl,

indenyltitaniumtriethyl,

indenyltitaniumtripropyl,

indenyltitaniumtriphenyl,

tetrahydroindenyltitaniumtribenzyl,

pentamethylcyclopentadienyltitaniumtriisopropyl,

pentamethylcyclopentadienyltitaniumtribenzyl,

pentamethylcyclopentadienyltitaniumdimethylmethoxide,

(η⁵-2,4-dimethyl-1,3-pentadienyl)titaniumtrimethyl,

octahydrofluorenyltitaniumtrimethyl,

tetrahydroindenyltitaniumtrimethyl,

tetrahydrofluorenyltitaniumtrimethyl,

(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl,

(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

(tert-butylamido)(hexamethyl-η⁵-indenyl)dimethylsilanetitanium dimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) allyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido) (2-methylindenyl)dimethylsilanetitanium (IV) dimethyl,

(tert-butylamido) (2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) 1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II ) 1,4-dibenzyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 3-methyl 1,3-pentadiene,

(tert-butylamido)(2,4-dimethyl-1,3-pentadien-2-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethylcyclopentadienyl)dimethylsilanetitanium1,3-pentadiene,

(tert-butylamido)(3-(N-pyrrolidinyl)inden-1-yl)dimethylsilanetitanium1,3-pentadiene,

(tert-butylamido)(2-methyl-s-indacen-1-yl)dimethylsilanetitanium1,3-pentadiene, and(tert-butylamido)(3,4-cyclopenta(/)phenanthren-2-yl)dimethylsilanetitanium1,4-diphenyl-1,3-butadiene.

Bis(L) containing complexes including bridged complexes suitable for usein the present invention include:

biscyclopentadienylzirconiumdimethyl,

biscyclopentadienylzirconiumdiethyl,

biscyclopentadienylzirconiumdiisopropyl,

biscyclopentadienylzirconiumdiphenyl,

biscyclopentadienylzirconium dibenzyl,

biscyclopentadienylzirconium-2,4-pentadienyl,

biscyclopentadienylzirconiummethylmethoxide,

bispentamethylcyclopentadienylzirconiumdimethyl,

bisindenylzirconiumdimethyl,

indenylfluorenylzirconiumdiethyl,

bisindenylzirconiummethyl(2-(dimethylamino)benzyl),

bisindenylzirconium methyltrimethylsilyl,

bistetrahydroindenylzirconium methyltrimethylsilyl,

bispentamethylcyclopentadienylzirconiumdiisopropyl,

bispentamethylcyclopentadienylzirconiumdibenzyl,

bispentamethylcyclopentadienylzirconiummethylmethoxide,

(dimethylsilyl-bis-cyclopentadienyl)zirconiumdimethyl,

(dimethylsilyl-bis-pentamethylcyclopentadienyl)zirconium-2,4-pentadienyl,

(methylene-bis-pentamethylcyclopentadienyl)zirconium(III)2-(dimethylamino)benzyl,

(dimethylsilyl-bis-2-methylindenyl)zirconiumdimethyl,

(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconiumdimethyl,

(dimethylsilyl-bis-2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,(dimethylsilyl-bis-tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

(dimethylsilyl-bis-tetrahydrofluorenyl)zirconiumdi(trimethylsilyl),

(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and

(dimethylsilylpentamethylcyclopentadienylfluorenyl)zirconiumdimethyl.

Suitable polymerizable monomers include ethylenically unsaturatedmonomers, acetylenic compounds, conjugated or non-conjugated dienes, andpolyenes. Preferred monomers include olefins, for examples alpha-olefinshaving from 2 to 20,000, preferably from 2 to 20, more preferably from 2to 8 carbon atoms and combinations of two or more of such alpha-olefins.Particularly suitable alpha-olefins include, for example, ethylene,propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,1-tetradecene, 1-pentadecene, or combinations thereof, as well as longchain vinyl terminated oligomeric or polymeric reaction products formedduring the polymerization, and C₁₀₋₃₀ α-olefins specifically added tothe reaction mixture in order to produce relatively long chain branchesin the resulting polymers. Preferably, the alpha-olefins are ethylene,propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene, andcombinations of ethylene and/or propene with one or more of such otheralpha-olefins. Other preferred monomers include styrene, halo- or alkylsubstituted styrenes, tetrafluoroethylene, vinylcyclobutene,1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and1,7-octadiene. Mixtures of the above-mentioned monomers may also beemployed.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for solution phase, slurry, gas phase and highpressure Ziegler-Natta or Kaminsky-Sinn type polymerization reactions.Examples of such well known polymerization processes are depicted in WO88/02009, U.S. Pat. Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652,4,543,399, 4,564,647, 4,522,987, and elsewhere. Preferred polymerizationtemperatures are from 0-250° C. Preferred polymerization pressures arefrom atmospheric to 3000 atmospheres. Molecular weight control agentscan be used in combination with the present cocatalysts. Examples ofsuch molecular weight control agents include hydrogen, silanes or otherknown chain transfer agents. The catalyst composition may be used byitself (homogeneously) or supported on an inert support such as silica,alumina or a polymer.

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis.Where stated, the term “room temperature” refers to a temperature from20 to 25° C., the term “overnight” refers to a time from 12 to 18 hours,and the term “mixed alkanes” refers to a mixture of propylene oligomerssold by Exxon Chemicals Inc. under the trade designation Isopar™ E.

EXAMPLES

Tris(perfluorophenyl)borane (FAB) was obtained as a solid from BoulderScientific Inc. and used without further purification. Modifiedmethalumoxane (MMAO-3A) in heptane was purchased from Akzo-Nobel. MAOand trimethylaluminum (TMA) both in toluene were purchased from AldrichChemical Co. Tris(perfluorophenyl)aluminum (FAAL) in toluene wasprepared by exchange reaction between tris(perfluorophenyl)borane andtrimethylaluminum. All solvents were purified using the techniquedisclosed by Pangborn et al, Organometallics, 1996, 15, 1518-1520. Allcompounds and solutions were handled under an inert atmosphere (drybox). All chemical shift for ¹⁹F NMR spectra were relative to a fixedexternal standard (CFCl₃) in benzene d₆ or toluene d₈, either of whichwere dried over N/K alloy and filtered prior to use. ¹H and ¹³C NMRshifts were referenced to internal solvent resonances and are reportedrelative to TMS.

Preparation of diisobutyl(2,6-di-t-butyl-4-methylphenoxy)aluminum(DIBAL-BOT) was conducted according to the method ofSkowronska-Ptasinska, M. et al., J. Organometallic Chem., 1978, 160,403-409. The product was isolated as a colorless oil. NMR spectroscopicdata are as follows: ¹H NMR (C₆D₆) δ7.08, 2.27(s,3H), 2.03, m, 1H, J=6.8Hz), 1.48 (s, 18H), 1.02 (d, 12H, J=6.8 Hz), 0.39 (d, 12H, J=6.8 Hz);¹³C NMR (C₆D₆) δ153.9, 138.1, 127.2, 126.0, 34.8, 32.1, 28.2, 25.8,24.0, 21.5. This product was used in the following ligand exchangereactions (Examples 1-5) to prepareisobutyl(pentafluorophenyl)(2,4-di-(t-butyl)4-methylphenoxy)aluminum.

Example 1

In a glove box, FAAL (0.012 g, 0.02 mmol, toluene adduct) and DIBAL-BOT(0.007 g, 0.02 mmol) were mixed in 0.7 ml of benzene-d₆ and the mixturewas loaded into a NMR tube. NMR spectra were recorded after mixing thesereagents in the NMR tube for 10 min.Isobutyl(pentfluorophenyl)(2,4-di-(t-butyl)-4-methylphenoxy)aluminum wasidentified in the reaction mixture along withisobutylbis(pentafluorophenyl)aluminum. After 4 more hours at roomtemperature, no significant change in products or ratios of products wasdetected.

Spectroscopic data fordi(isobutyl)(2,6-di-(t-butyl)-4-methylphenoxy)aluminum): ¹H NMR (C₆D₆,23° C.): δ7.10 (s, 2H, Ar), 2.25 (s, 3H, Ar—CH₃), 1.89 (septet,J_(H-H)=6.6 Hz, 1H, Me₂CHCH₂—),1.50 (s, 18H, tBu), 0.89 (d, J_(H-H)=6.6Hz, 6H, Me₂CHCH₂—), 0.50 (d, J_(H-H)=7.2Hz, 2H , Me₂CHCH₂—). ¹⁹F NMR(C₆D₆, 23° C.): δ−120.93 (dd, ³J_(F-F)=18.3 Hz, 2 F, o-F), −149.65 (t,³J_(F-F)=21.4 Hz, 1 F, p-F), −159.61 (tt, ³J_(F-F)=24.5 Hz, 2F, m-F).

Example 2

The reaction conditions of Example 1 were substantially repeated using amolar ratio of FAAL to DIBAL-BOT of 1:3. Accordingly, in a glove box,FAAL (0.006 g, 0.01 mmol, toluene adduct) and DIBAL-BOT (0.011 g, 0.03mmol) were mixed in 0.7 ml of benzene-d₆ and the mixture was loaded intoa NMR tube. NMR spectra were recorded after mixing for 15 min.Isobutyl(pentafluorophenyl)(2,6-di-tert-butyl-4-methylphenoxy)aluminumand a minor amount of a dimer of isobutylbis(pentafluorophenyl)aluminumwith diisobutyl(pentafluorophenyl)aluminum were found to form from theexchange. There was no FAAL reagent left in the reaction mixture. Nosignificant change in product mix was detected after 4 h reaction.

Example 3

The reaction conditions of Example 1 were substantially repeated usingFAB and DIBAL-BOT in a molar ratio of 1:3. Accordingly, in a glove box,FAB (0.01 g, 0.02 mmol) and DIBAL-BOT (0.022 g, 0.06 mmol) were mixed in0.7 ml of benzene-d₆ and the mixture was loaded into a NMR tube. NMRspectra were recorded after mixing these reagents in the NMR tube for 30min.Isobutylpentafluorophenyl(2,6-di-tert-butyl-4-methylphenoxy)aluminumalong with quantities of diisobutylpentafluorophenylboron,triisobutylboron, andisobutyldi(2,6-di-tert-butyl-4-methylphenoxy)aluminum were found to formfrom the exchange. There was no FAB reagent left in the reactionmixture. After continued reaction for 12 h alldiisobutylpentafluorophenylboron disappeared, giving a product mixturecomprising triisobutylboron andisobutylpentafluorophenyl(2,6-di-(t-butyl)-4-methylphenoxy)aluminum.

/BU₂B(C₆F₅) ¹H NMR (C₆D₆, 23° C.): δ0.82 (d, J_(H-H)=6.6 Hz, 6H ,Me₂CHCH₂—) and the rest of the resonances are overlapping with otherspecies. ¹⁹F NMR (C₆D₆, 23° C.): δ−134.18 (dd, ³J_(F-F)=24.4 Hz, 2 F,o-F), −153.17 (t, ³J_(F-F)=21.2 Hz, 1 F, p-F), −161.56 (tt,³J_(F-F)=24.3 Hz, 2 F, m-F). /Bu₃B ¹H NMR (C₆D₆, 23° C.): δ0.92 (d,J_(H-H)=6.6 Hz, 6H, Me₂CHCH₂—) and the rest of the resonances areoverlapping with other species.

Example 4

The reaction conditions of Example 3 were substantially repeated usingFAB and DIBAL-BOT in a molar ratio of 1:10. Accordingly, in a glove box,FAB (0.005 g, 0.01 mmol) and DIBAL-BOT (0.036 g, 0.10 mmol) were mixedin 0.7 ml of benzene-d₆ and the mixture was loaded into a NMR tube. NMRspectra were recorded after mixing these reagents in the NMR tube for 15min. The major identified species wereisobutylpentafluorophenyl(2,6-di-(t-butyl)-4-methylphenoxy)aluminum andtriisobutylboron, with smaller amounts ofisobutyldi(2,6-di-(t-butyl)-4-methylphenoxy)aluminum and the dimer ofisobutylbis(pentafluorophenyl)aluminum anddiisobutylpentafluorophenylaluminum. There was no FAB reagent left inthe reaction mixture.

Example 5

In a glove box, FAAL (0.012 g, 0.02 mmol, toluene adduct) anddimethyl(2,6-di(t-butyl)-4-methylphenoxy)aluminum (DIMAL-BOT) (0.006 g,0.02 mmol) were mixed in 0.7 ml of benzene-d₆ and the mixture was loadedinto a NMR tube. NMR spectra were recorded after mixing these reagentsin the NMR tube for 1 h. An equilibrium mixture including startingcompounds,methyl(pentafluorophenyl)(2,6-di(t-butyl)-4-methylphenoxy)aluminum,bis(pentafluorophenyl)(2,6-di(t-butyl)-4-methylphenoxy)aluminum thedimer of methyl(bispentafluorophenyl)aluminum anddimethylpentafluorophenylaluminum were identified.

Me(C₆F₅)Al(BHT) ¹H NMR (C₆D₆, 23° C.): δ7.10 (s, 2H, Ar), 2.25 (s, 3H,Ar—CH₃), 1.46 (s, 18H , tBu), −0.28 (s, 3H , MeAl). ¹⁹F NMR (C₆D₆, 23°C.): δ−121.29 (d, ³J_(F-F)=18.3 Hz, 2 F, o-F), −149.82 (t, ³J_(F-F)=21.4Hz, 1 F, p-F), −159.99 (tt, ³J_(F-F)=24.5 Hz, 2 F, m-F). C₆F₅)₂Al(BHT)¹H NMR (C₆D₆, 23° C.): δ7.13 (s, 2H , Ar), 2.28 (s, 3H, Ar—CH₃), 1.52(s, 18H , tBu). ¹⁹F NMR (C₆D₆, 23° C.): δ−121.06((dd, ³J_(F-F)=18.3 Hz,2 F, o-F), −147.35 (t, ³J_(F-F)=21.4 Hz, 1 F, p-F), −159.15 (tt,³J_(F-F)=24.5 Hz, 2 F, m-F).

Polymerizations

A 2-liter Parr reactor was used in the polymerizations. All feeds werepassed through columns of alumina and a decontaminant (Q-5 catalystavailable from Englehardt Chemicals Inc.) prior to introduction into thereactor. Catalyst and cocatalysts are handled in a glovebox containingan atmosphere of argon or nitrogen.

A stirred 2.0 liter reactor is charged with about 740 g of mixed alkanessolvent and 118 g of 1-octene comonomer. Hydrogen is added as amolecular weight control agent by differential pressure expansion from a75 ml addition tank at 25 psi (2070 kPa). The reactor is heated to thepolymerization temperature of 130° C. and saturated with ethylene at 500psig (3.4 MPa). FAAL or FAB are combined withdiisobutyl(2,6-di-(t-butyl)-4-methylphenoxy)aluminum as toluenesolutions and allowed to stand at 25° C. for 15 minutes prior to use.Catalyst(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium1,3-pentadiene) and the indicated cocatalyst, as dilute solutions intoluene, are mixed at a ratio from 1:1 to 1:10, transferred to acatalyst addition tank, and injected into the reactor. Thepolymerization conditions are maintained for 15 minutes with ethyleneadded on demand. The resulting solution is removed from the reactor,quenched with isopropanol and stabilized by addition of 10 ml of atoluene solution containing approximately 67 mg of a hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and 133 mg of aphosphorus stabilizer (Irgafos™ 168 from Ciba Geigy Corporation.

Between polymerization runs a wash cycle in which 850 g of mixed alkanesis added to the reactor and the reactor heated to 150° C. The reactor isemptied of the heated solvent immediately before beginning a newpolymerization run.

Polymers are recovered by drying in a vacuum oven set at 140° C. forabout 20 hours. Density values are derived by determining the polymer'smass when in air and when immersed in methylethylketone. Micro meltindex values (MMI) are obtained using a “Custom Scientific InstrumentInc. Model CS-127MF-015” apparatus at 190° C. MMI (micro-melt index) areunit-less values calculated as follows: MMI=1/(0.00343 t −0.00251),where t=time in seconds. Results are contained in Table 1.

TABLE 1 μmoles Efficiency g catalyst/ Exotherm Yield polymer/μg DensityRun Activator(s) activator** (° C.) (g) Ti g/ml MMI 1 FAAL/Dibal-Bot0.75/3/15 1.4 20.9 0.58 0.904 0.5 2 FAAL/Dibal-Bot 1/4/8 1.9 25.4 0.530.904 0.5 3 FAAL/Dibal-Bot 0.75/3/3 5.2 68.6 1.91 0.905 1.2 4FAB/Dibal-Bot 1/1/10 2.6 53.0 1.11 0.901 3.7 A* FAB 1.5/1.5 1.3 48.70.68 0.901 9.3 B* FAAL 0.5/0.5 0.0 0.9 0.038 — — C* FAAL 0.25/1 1.3 0.1— — — *comparative example, not an example of the invention. **Catalystratios reflect metal complex: first activator:second activator

Popylene Homopolymerization

The above polymerization conditions were substantially repeatedexcepting the 250 g of mixed alkanes solvent and 300 g of propylene arepolymerized at a polymerization temperature of 70° C.

The cocatalyst was prepared by combining FAB withdiisobutyl(2,6-di-(t-butyl)-4-methylphenoxy)aluminum in a molar ratio of1:10 and allowing the mixture to stand at 25° C. for 15 minutes. Themixture was not devolatilized to remove triisopropylborane byproducts.Catalyst, dimethylsilanebis(2-methyl-4-phenylindenyl)zirconium1,4-diphenyl-1,3-butadiene (1.0 μmole) and the indicated cocatalyst, asdilute solutions in toluene, are then mixed at a ratio from 1:1:10(zirconium complex: FAB: DIBAL-BOT), transferred to a catalyst additiontank, and injected into the reactor. The polymerization conditions aremaintained for 15 minutes. The resulting solution is removed from thereactor, quenched with isopropyl alcohol, and stabilized by addition of10 ml of a toluene solution containing approximately 67 mg of a hinderedphenol antioxidant (Irganox™ from Ciba Geigy Corporation) and 133 mg ofa phosphorus stabilizer (Irgafos 168 Ciba Geigy Corporation). 63.2 g ofisotactic polypropylene having Tm of 156° C., Mw=250,000, a molecularweight distribution (Mw/Mn) of 2.05 are recovered. Catalyst efficiencyis 0.7 Kg/mg Zr.

What is claimed is:
 1. A catalyst composition comprising a Group 3-10metal complex and an activator compound corresponding to the formula:AlAr^(f)Q¹Q²; where: Ar^(f) is a fluorinated aromatic hydrocarbyl moietyof from 6 to 30 carbon atoms; Q¹ is Ar^(f) or a C₁₋₂₀ hydrocarbyl group,or a C₁₋₂₀ hydrocarbyl group substituted with one or morecyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl,di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino,di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to20 atoms other than hydrogen, or such substituent groups may becovalently linked with each other to form one or more fused rings orring systems; and Q² is an aryloxy, arylsulfideo or di(hydrocarbyl)amidogroup, or such group substituted with one or more hydrocarbyl,cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl,di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino,di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to20 atoms other than hydrogen, or such substituent groups may becovalently linked with each other to form one or more fused rings orring systems, said Q² having from 3 to 20 atoms other than hydrogen. 2.A composition according to claim 1 wherein Ar^(f) each occurrence isperfluorophenyl.
 3. A composition according to claim 1 wherein Ar^(f) ispentafluorophenyl, Q¹ is isobutyl, and Q² is 2,6-di-(t-butyl)phenoxy,2,6-di-(t-butyl)-4-methylphenoxy, N,N-bis(trimethylsilyl)amido, orN,N-dimethylamido.
 4. A composition according to claim 1 wherein Ar^(f)is pentafluorophenyl, Q¹ is isobutyl, and Q² is4-methyl-2,6-di-t-butylphenoxy.
 5. A composition of any of claims 1-4wherein the metal complex is a Group 4 metal complex.
 6. The compositionof claim 5 wherein the molar ratio of metal complex to activatorcompound is from 0.1:1 to 2:1.
 7. The composition of claim 5additionally comprising a support material in the form of a particulatedsolid.
 8. The composition of claim 5 wherein the metal complex is:(tert-butylamido)(tetramethylcyclopentadienyl)dimethylsilanetitaniumdimethyl,(tert-butylamido)(tetramethylcyclopentadienyl)dimethylsilanetitanium1,3-pentadiene,(tert-butylamido)(2-methyl-s-indacen-1-yl)dimethylsilanetitanium1,3-pentadiene,(tert-butylamido)(3-(N-pyrrolidinyl)inden-1-yl)dimethylsilanetitanium1,3-pentadiene,(tert-butylamido)(3,4-cyclopenta(l)phenanthren-2-yl)dimethylsilanetitanium1,4-diphenyl-1,3-butadiene,(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium dimethyl,(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium1,4-diphenyl-1,3-butadiene, (1,2-ethanediyl)bis(inden-1-yl)zirconiumdimethyl, or (1,2-ethanediyl)bis(inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene.